Diaqua-bis(4-methyl-benzoato-κO)bis-(nicotinamide-κN)manganese(II).

In the mononuclear title complex, [Mn(C(8)H(7)O(2))(2)(C(6)H(6)N(2)O)(2)(H(2)O)(2)], the Mn(II) ion is located on a crystallographic inversion center. The asymmetric unit contains one 4-methyl-benzoate anion, one nicotinamide (NA) ligand and one coordinated water mol-ecule. The four O atoms in the equatorial plane around the Mn(II) ion form a slightly distorted square-planar arrangement, while the slightly distorted octa-hedral coordination is completed by the two pyridine N atoms of the NA ligands in the axial positions. The dihedral angle between the carboxyl-ate group and the attached benzene ring is 9.01 (7)°, while the pyridine and benzene rings are oriented at a dihedral angle of 42.44 (5)°. In the crystal structure, inter-molecular O-H⋯O, N-H⋯O and C-H⋯O hydrogen bonds, and O-H⋯π and C-H⋯π inter-actions link the mol-ecules into a two-dimensional network parallel to (001).

Related literature

For niacin, see: Krishnamachari (1974 ▶), and for the n class="Chemical">nicotinic acid derivative N,N-diethyl­nicotinamide, see: Bigoli et al. (1972 ▶). For related structures, see: Hökelek et al. (1996 ▶, 2009a ▶,b ▶,c ▶); Hökelek & Necefoğlu (1998 ▶); Necefoğlu et al. (2010 ▶).

Experimental

Crystal data

[Mn(C8H7O2)2(C6H6N2O)2(n class="Chemical">H2O)2]

M = 605.51

Triclinic,

a = 7.3289 (2) Å

b = 10.1768 (3) Å

c = 10.6292 (3) Å

α = 66.852 (2)°

β = 78.232 (4)°

γ = 70.206 (3)°

V = 683.58 (4) Å3

Z = 1

Mo Kα radiation

μ = 0.54 mm−1

T = 100 K

0.38 × 0.25 × 0.19 mm

Data collection

Bruker Kappa APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T min = 0.649, T max = 0.698

11619 measured reflections

3297 independent reflections

3022 reflections with I > 2σ(I)

R int = 0.028

Refinement

R[F 2 > 2σ(F 2)] = 0.035

wR(F 2) = 0.099

S = 1.08

3297 reflections

204 parameters

3 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.73 e Å−3

Δρmin = −0.38 e Å−3

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAIn class="Chemical">NT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶) and PLATON (Spek, 2009 ▶).

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810011815/ci5069sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810011815/ci5069Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

[Mn(C8H7O2)2(C6H6N2O)2(H2O)2]	Z = 1
Mr = 605.51	F(000) = 315
Triclinic, P1	Dx = 1.471 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.3289 (2) Å	Cell parameters from 8087 reflections
b = 10.1768 (3) Å	θ = 2.5–28.4°
c = 10.6292 (3) Å	µ = 0.54 mm−1
α = 66.852 (2)°	T = 100 K
β = 78.232 (4)°	Block, colourless
γ = 70.206 (3)°	0.38 × 0.25 × 0.19 mm
V = 683.58 (4) Å3

Bruker Kappa APEXII CCD area-detector diffractometer	3297 independent reflections
Radiation source: fine-focus sealed tube	3022 reflections with I > 2σ(I)
graphite	Rint = 0.028
φ and ω scans	θmax = 28.4°, θmin = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −9→9
Tmin = 0.649, Tmax = 0.698	k = −11→13
11619 measured reflections	l = −14→14

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.099	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	w = 1/[σ2(Fo2) + (0.058P)2 + 0.3059P] where P = (Fo2 + 2Fc2)/3
3297 reflections	(Δ/σ)max = 0.001
204 parameters	Δρmax = 0.73 e Å−3
3 restraints	Δρmin = −0.38 e Å−3

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

	x	y	z	Uiso*/Ueq
Mn1	0.0000	0.0000	0.0000	0.01276 (11)
O1	0.24237 (17)	−0.33733 (12)	0.25988 (12)	0.0207 (2)
O2	0.16077 (17)	−0.08763 (12)	0.17238 (12)	0.0201 (2)
O3	0.78404 (16)	−0.34130 (13)	−0.01469 (13)	0.0210 (3)
O4	0.18323 (19)	0.15102 (14)	−0.09400 (13)	0.0232 (3)
H41	0.208 (4)	0.190 (3)	−0.1860 (17)	0.064 (9)*
H42	0.218 (4)	0.205 (3)	−0.058 (2)	0.042 (7)*
N1	0.21166 (18)	−0.15932 (14)	−0.10409 (13)	0.0143 (3)
N2	0.84692 (19)	−0.50868 (14)	−0.11834 (14)	0.0167 (3)
H21	0.810 (3)	−0.555 (3)	−0.159 (2)	0.028 (5)*
H22	0.958 (4)	−0.545 (3)	−0.084 (2)	0.032 (6)*
C1	0.2620 (2)	−0.21470 (17)	0.24423 (15)	0.0151 (3)
C2	0.4196 (2)	−0.21314 (16)	0.31505 (15)	0.0145 (3)
C3	0.4331 (2)	−0.07942 (16)	0.31453 (15)	0.0164 (3)
H3	0.3426	0.0099	0.2714	0.020*
C4	0.5805 (2)	−0.07856 (18)	0.37770 (16)	0.0181 (3)
H4	0.5871	0.0115	0.3767	0.022*
C5	0.7191 (2)	−0.21079 (19)	0.44279 (16)	0.0190 (3)
C6	0.7063 (2)	−0.34413 (18)	0.44183 (16)	0.0203 (3)
H6	0.7979	−0.4333	0.4839	0.024*
C7	0.5589 (2)	−0.34546 (17)	0.37902 (16)	0.0177 (3)
H7	0.5528	−0.4355	0.3795	0.021*
C8	0.8783 (3)	−0.2097 (2)	0.51214 (18)	0.0257 (4)
H8A	0.8947	−0.1115	0.4763	0.039*
H8B	0.9977	−0.2797	0.4951	0.039*
H8C	0.8437	−0.2371	0.6092	0.039*
C9	0.3975 (2)	−0.22336 (16)	−0.07444 (15)	0.0132 (3)
H9	0.4418	−0.1971	−0.0142	0.016*
C10	0.5280 (2)	−0.32707 (16)	−0.12893 (15)	0.0134 (3)
C11	0.4623 (2)	−0.36415 (17)	−0.22143 (16)	0.0170 (3)
H11	0.5453	−0.4328	−0.2602	0.020*
C12	0.2710 (2)	−0.29647 (18)	−0.25420 (17)	0.0198 (3)
H12	0.2239	−0.3182	−0.3164	0.024*
C13	0.1508 (2)	−0.19621 (17)	−0.19343 (16)	0.0172 (3)
H13	0.0221	−0.1523	−0.2153	0.021*
C14	0.7300 (2)	−0.39401 (16)	−0.08365 (15)	0.0142 (3)

	U11	U22	U33	U12	U13	U23
Mn1	0.01065 (17)	0.01054 (16)	0.01760 (17)	0.00071 (11)	−0.00334 (11)	−0.00758 (12)
O1	0.0252 (6)	0.0149 (5)	0.0241 (6)	−0.0030 (4)	−0.0062 (5)	−0.0092 (5)
O2	0.0216 (6)	0.0138 (5)	0.0243 (6)	0.0035 (4)	−0.0106 (5)	−0.0092 (4)
O3	0.0160 (5)	0.0184 (5)	0.0343 (6)	0.0021 (4)	−0.0096 (5)	−0.0174 (5)
O4	0.0308 (7)	0.0236 (6)	0.0233 (6)	−0.0146 (5)	0.0056 (5)	−0.0147 (5)
N1	0.0126 (6)	0.0117 (6)	0.0177 (6)	−0.0003 (4)	−0.0030 (5)	−0.0061 (5)
N2	0.0120 (6)	0.0146 (6)	0.0258 (7)	0.0020 (5)	−0.0057 (5)	−0.0125 (5)
C1	0.0149 (7)	0.0150 (7)	0.0155 (7)	0.0004 (5)	−0.0019 (5)	−0.0091 (6)
C2	0.0147 (7)	0.0137 (7)	0.0140 (6)	−0.0008 (5)	−0.0017 (5)	−0.0061 (5)
C3	0.0175 (7)	0.0129 (7)	0.0164 (7)	−0.0004 (5)	−0.0029 (6)	−0.0055 (6)
C4	0.0209 (8)	0.0181 (7)	0.0173 (7)	−0.0059 (6)	−0.0014 (6)	−0.0080 (6)
C5	0.0170 (7)	0.0245 (8)	0.0158 (7)	−0.0045 (6)	−0.0017 (6)	−0.0083 (6)
C6	0.0182 (7)	0.0177 (7)	0.0196 (7)	0.0026 (6)	−0.0066 (6)	−0.0053 (6)
C7	0.0203 (7)	0.0124 (7)	0.0186 (7)	−0.0006 (5)	−0.0041 (6)	−0.0056 (6)
C8	0.0199 (8)	0.0352 (10)	0.0240 (8)	−0.0067 (7)	−0.0061 (6)	−0.0114 (7)
C9	0.0137 (7)	0.0105 (6)	0.0160 (6)	−0.0017 (5)	−0.0027 (5)	−0.0060 (5)
C10	0.0118 (7)	0.0101 (6)	0.0174 (7)	−0.0007 (5)	−0.0031 (5)	−0.0051 (5)
C11	0.0146 (7)	0.0149 (7)	0.0224 (7)	0.0015 (5)	−0.0042 (6)	−0.0110 (6)
C12	0.0181 (8)	0.0194 (7)	0.0258 (8)	0.0016 (6)	−0.0092 (6)	−0.0142 (7)
C13	0.0137 (7)	0.0150 (7)	0.0229 (7)	0.0008 (5)	−0.0059 (6)	−0.0087 (6)
C14	0.0127 (7)	0.0113 (6)	0.0184 (7)	−0.0007 (5)	−0.0033 (5)	−0.0063 (5)

Mn1—O2	2.1036 (11)	C4—C3	1.387 (2)
Mn1—O2i	2.1036 (11)	C4—C5	1.396 (2)
Mn1—O4	2.1924 (12)	C4—H4	0.93
Mn1—O4i	2.1924 (12)	C5—C8	1.507 (2)
Mn1—N1	2.2947 (13)	C6—C5	1.396 (2)
Mn1—N1i	2.2947 (13)	C6—C7	1.387 (2)
O1—C1	1.2466 (19)	C6—H6	0.93
O2—C1	1.2690 (18)	C7—H7	0.93
O3—C14	1.2464 (18)	C8—H8A	0.96
O4—H41	0.905 (16)	C8—H8B	0.96
O4—H42	0.906 (16)	C8—H8C	0.96
N1—C9	1.3386 (18)	C9—C10	1.391 (2)
N1—C13	1.345 (2)	C9—H9	0.93
N2—C14	1.3283 (19)	C11—C10	1.396 (2)
N2—H21	0.89 (2)	C11—C12	1.385 (2)
N2—H22	0.86 (2)	C11—H11	0.93
C1—C2	1.509 (2)	C12—H12	0.93
C2—C3	1.395 (2)	C13—C12	1.383 (2)
C2—C7	1.397 (2)	C13—H13	0.93
C3—H3	0.93	C14—C10	1.4956 (19)
O2—Mn1—O2i	180.00 (4)	C3—C4—H4	119.5
O2—Mn1—O4	86.18 (5)	C5—C4—H4	119.5
O2i—Mn1—O4	93.82 (5)	C4—C5—C8	120.94 (15)
O2—Mn1—O4i	93.82 (5)	C6—C5—C4	118.20 (14)
O2i—Mn1—O4i	86.18 (5)	C6—C5—C8	120.86 (15)
O2—Mn1—N1i	86.02 (4)	C5—C6—H6	119.5
O2i—Mn1—N1i	93.98 (4)	C7—C6—C5	120.91 (14)
O2—Mn1—N1	93.98 (4)	C7—C6—H6	119.5
O2i—Mn1—N1	86.02 (4)	C2—C7—H7	119.6
O4—Mn1—O4i	180.00 (5)	C6—C7—C2	120.74 (14)
O4—Mn1—N1i	91.32 (4)	C6—C7—H7	119.6
O4i—Mn1—N1i	88.68 (4)	C5—C8—H8A	109.5
O4—Mn1—N1	88.68 (4)	C5—C8—H8B	109.5
O4i—Mn1—N1	91.32 (4)	C5—C8—H8C	109.5
N1i—Mn1—N1	180.00 (9)	H8A—C8—H8B	109.5
C1—O2—Mn1	136.86 (10)	H8A—C8—H8C	109.5
Mn1—O4—H41	122.2 (18)	H8B—C8—H8C	109.5
Mn1—O4—H42	129.2 (16)	N1—C9—C10	123.52 (13)
H42—O4—H41	107 (2)	N1—C9—H9	118.2
C9—N1—Mn1	121.52 (10)	C10—C9—H9	118.2
C9—N1—C13	117.56 (13)	C9—C10—C11	118.15 (13)
C13—N1—Mn1	120.88 (10)	C9—C10—C14	118.12 (13)
C14—N2—H21	124.4 (15)	C11—C10—C14	123.72 (13)
C14—N2—H22	113.3 (16)	C10—C11—H11	120.7
H21—N2—H22	121 (2)	C12—C11—C10	118.59 (14)
O1—C1—O2	125.89 (14)	C12—C11—H11	120.7
O1—C1—C2	118.59 (13)	C11—C12—H12	120.4
O2—C1—C2	115.51 (13)	C13—C12—C11	119.26 (14)
C3—C2—C1	120.90 (13)	C13—C12—H12	120.4
C3—C2—C7	118.51 (14)	N1—C13—C12	122.90 (14)
C7—C2—C1	120.56 (13)	N1—C13—H13	118.6
C2—C3—H3	119.7	C12—C13—H13	118.6
C4—C3—C2	120.59 (14)	O3—C14—N2	121.84 (14)
C4—C3—H3	119.7	O3—C14—C10	119.46 (13)
C3—C4—C5	121.05 (14)	N2—C14—C10	118.71 (13)
O4—Mn1—O2—C1	−124.12 (16)	O2—C1—C2—C7	−169.99 (14)
O4i—Mn1—O2—C1	55.88 (16)	C1—C2—C3—C4	−178.83 (14)
N1i—Mn1—O2—C1	144.28 (16)	C7—C2—C3—C4	−0.8 (2)
N1—Mn1—O2—C1	−35.72 (16)	C1—C2—C7—C6	178.70 (15)
O2—Mn1—N1—C9	−23.31 (12)	C3—C2—C7—C6	0.6 (2)
O2i—Mn1—N1—C9	156.69 (12)	C5—C4—C3—C2	0.2 (2)
O2—Mn1—N1—C13	154.04 (12)	C3—C4—C5—C6	0.4 (2)
O2i—Mn1—N1—C13	−25.96 (12)	C3—C4—C5—C8	−179.60 (15)
O4—Mn1—N1—C9	62.76 (11)	C5—C6—C7—C2	0.0 (2)
O4i—Mn1—N1—C9	−117.24 (11)	C7—C6—C5—C4	−0.6 (2)
O4—Mn1—N1—C13	−119.89 (12)	C7—C6—C5—C8	179.46 (15)
O4i—Mn1—N1—C13	60.11 (12)	N1—C9—C10—C11	1.2 (2)
Mn1—O2—C1—O1	−26.6 (3)	N1—C9—C10—C14	−177.98 (13)
Mn1—O2—C1—C2	153.01 (12)	C12—C11—C10—C9	−0.1 (2)
Mn1—N1—C9—C10	176.18 (11)	C12—C11—C10—C14	179.01 (15)
C13—N1—C9—C10	−1.3 (2)	C10—C11—C12—C13	−0.8 (2)
Mn1—N1—C13—C12	−177.22 (13)	N1—C13—C12—C11	0.8 (3)
C9—N1—C13—C12	0.2 (2)	O3—C14—C10—C9	−9.9 (2)
O1—C1—C2—C3	−172.31 (14)	O3—C14—C10—C11	170.95 (15)
O1—C1—C2—C7	9.7 (2)	N2—C14—C10—C9	170.04 (14)
O2—C1—C2—C3	8.0 (2)	N2—C14—C10—C11	−9.1 (2)

Cg1 and Cg2 are the centroids of the C2-C7 andN1/C9-C13 rings, respectively.

D—H···A	D—H	H···A	D···A	D—H···A
N2—H21···O1ii	0.88 (3)	1.97 (3)	2.8456 (19)	174 (2)
N2—H22···O3iii	0.86 (3)	2.09 (3)	2.952 (2)	172 (3)
O4—H42···O3iv	0.90 (3)	1.83 (3)	2.7071 (19)	164 (3)
C11—H11···O1ii	0.93	2.33	3.200 (2)	156
O4—H41···Cg1v	0.91 (2)	2.33 (2)	3.141 (2)	149 (3)
C4—H4···Cg2v	0.93	2.80	3.490 (2)	132

Table 1

Selected bond lengths (Å)

Mn1—O2	2.1036 (11)
Mn1—O4	2.1924 (12)
Mn1—N1	2.2947 (13)

Table 2

Hydrogen-bond geometry (Å, °)

Cg1 and Cg2 are the centroids of the C2-C7 andN1/C9-C13 rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H21⋯O1i	0.88 (3)	1.97 (3)	2.8456 (19)	174 (2)
N2—H22⋯O3ii	0.86 (3)	2.09 (3)	2.952 (2)	172 (3)
O4—H42⋯O3iii	0.90 (3)	1.83 (3)	2.7071 (19)	164 (3)
C11—H11⋯O1i	0.93	2.33	3.200 (2)	156
O4—H41⋯Cg1iv	0.91 (2)	2.33 (2)	3.141 (2)	149 (3)
C4—H4⋯Cg2iv	0.93	2.80	3.490 (2)	132

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) .